Methods of detoxifying poisonous compounds



Patented Dec. 19, 1950 METHODS OF DETOXIFYING POISONOUS COMPOUNDS ArnoBrasch, Brooklyn, N. Y., assignor, by mesne assignments, to ElectronizedChemicals Corporation, New York, N. Y., a corporation of Delaware NoDrawing. Application September 24, 1947, Serial No. 775,883

14 Claims. (Cl. 99-69) This application is a continuation-in-part of myU. S. patent applications Serial No. 442,136, filed May 7, 1 42, nowabandoned, for Method for Manufacturing Synthetic Rubber and DevicesTherefor; Serial No. 442,137, filed May 7, 1942, now Patent No.2,429,217, for Devices for Treatment of Matters with High SpeedElectrons; Serial No. 442,138, filed May 7, 1942, now abandoned, forMethod for Treatment of Matters; Serial No. 450,923, filed July 14,1942, now abandoned, for Method and Means for Treatment of PerishableSubstances and Products so Obtained; Serial No. 451,370, filed July 17,1942, now abandoned, for Method and Means for Treatment of VegetativeSubstances and Products so Obtained; Serial No. 487,179, filed May 15,1943, now abandoned, for Process for Cracking Hydrocarbons by Means ofUltra High Speed Electrons; Serial No. 488,278, filed May 24, 1943, nowabandoned, for Preparation and Cracking of Hydrocarbons and OtherChemical Compounds by Means of Ultra High Speed Electrons to ObtainRubber Starting Materials; and Serial No. 575,878, filed Februar 2,1945, for Sterilization of Therapeutical Preparations.

My present'invention relates to methods of detoxifying stimulant andpoisonous compounds contained in products for human and animalconsumption.

It is an object of my present invention to provide methods of treatingproducts for human and animal consumption such as coffee, tea, tobaccoand the like in order to detoxify, e. g. destroy or decompose partly orwholly the stimulant and poisonous substances contained therein so as torender them harmless without essentially impairing the taste. flavor andappearance of the treated products.

More particularly, it is an object of my present invention to providemethods for detoxifying, e. g. by decomposing partly or entirelyalkaloids such as nicotine, caffeine and theine contained in tobacco,coffee and tea, respectively, so as to remove their stimulant andpoisonous character without influencing the appearance, flavor and tasteof the treated alkaloid-containing products.

With the above objects in view, my present invention mainly consists intreating the above mentioned products with corpuscular rays,particularly high speed electrons having a substantial penetration rangeso as to destroy, decompose or transform the stimulant and poisonoussubstances, particularly alkaloids contained in the treated productswithout noticeably attacking or influencing the other desiredcharacteristics of such products.

My present invention is based upon the discovery that corpuscular rays,particularly high speed electrons, have a highly differentiated andselective action, e. g. they attack only certain ingredients of thetreated products without infinancing the others.

In the case of stimulant and poisonous substances to be destroyed,particularly in the case of alkaloids, it is mainly a matter ofdecomposing the radiation labile molecules of the dangerous alkaloids orof substantially changing their nature by transforming them intonon-stimulant and non-poisonous compounds so as to eliminate theirstimulant and poisonous effects. I have found that bombardment withcorpuscular particles, particularly high speed electrons, in accordancewith my present invention, has the effects set forth above.

Thus, for instance, in the case of coffee, caffeine which is a basicalkaloid having highly unstable properties, is more apt to be influencedby the differentiated and selective action of the high speed electronsused in accordance with nix present invention than the more stablestances that give coffee its characteristic taster flavor, andappearance.

I wish to note that the term products" and products containingstimulants and poisonous compounds, as used above and in the followingdescription and claims, are intended to cover all types of products,particularly products for human use, e. g. consumption, which containpoisonous and/or stimulant compounds adapted to be selectively attackedby electron bombardment.

In order to obtain the objects of my present invention, i. e. in orderto destroy alkaloids contained in products of the type set forth above,it is of particular advantage to use high speed electrons of a velocityequivalent to more than one million volts. Although such electronbombardment can be carried out in many different ways with excellentresults, I noticed that by bombarding certain products for aconsiderable time with high speed electrons certain changes in taste,odor, appearance and structure were caused.

I have found that these changes are caused by certain side reactionswhich consist mainly in creation of hydrogen peroxide, ozone,denaturation of the proteins present in certain foodstuffs,decarboxylation, and hydrolysis of certain electron bombarded productsto be detoxified.

I have found that the side reactions mentioned in the precedingparagraph are mainly due to the interactions of the electrons with theatmosphere surrounding the electron bombarded products to be detoxifiedand the reactive compounds within these products, to the production ofheat and other related factors, and not due to the action of the highspeed electrons proper.

I have also found that these side reactions can be reduced by shorteningthe time periods during which the products, e. g. coffee, tea, andtobacco, are irradiated. Therefore, processes according to my presentinvention mainly consist in irradiating the products to be detoxifledwith high speed electrons during one or more extremely I short timeperiod. Such reduction of the length of the single irradiation periodsresults in reduction or avoidance of the above listed undesired sidereactions.

Furthermore, it is often important to avoid creation of heat in theirradiated products to be detoxified; this object is also attained byreducing .the length of the single irradiation periods.

I have obtained very good results by using for detoxifyin purposes highspeed electrons of a velocity equivalent to more than two, preferably,more than four million volts; excellent results were obtained by use ofhigh speed electrons of a velocity equivalent to about six millionvolts.

Furthermore, I have found it advisable to reduce the single irradiationperiods to less than preferably to about 10- of a second. In some cases,it will even be indicated to use irradiation periods each lasting 10* ofa second, or less.

I wish to emphasize that the short duration of the single irradiationperiods does not change the effectof such irradiations on the alkaloidscontained in the irradiated products to be detoxifled; I have found thatsuch irradiations have a detoxifying effect, i. e. decompose thealkaloids, inasmuch as such alkaloids need not be decomposed entirelyduring a single irradiation period, but only be vigorously attacked,such attacks, particularly if repeated during consecutive shortirradiation periods, decompose the alkaloids which will then lose theirstimulant and poisonous character a certain time after the irradiationsare actually terminated.

Thus, it is evident that the length of each of the single irradiationperiods is of minor importance from the point of view of decompositionof alkaloids, but that only the total length of irradiation periodstogether decides the irtion effect.

Therefore, in order to obtain optimal detoxification effects, I propose,in accordance with my present invention, to irradiate the products to bedetoxified with high speed electrons during a series of consecutiveshort time periods.

Preferably, the high speed electrons have a velocity equivalent to morethan four million volts, e. g. about six million volts, and theirradiation periods have each a length of less than 10' of a second, e.g. of about 10- of a second.

The number of single irradiation periods needed depends upon thecharacter of the irradiated product; thus, it is necessary that on theaverage each alkaloid particle in the product to be detoxifled is hitduring one or a series of consecutive short irradiation periods togetherby electrons having a total intensity of about 10* of a watt.

I have found that the above mentioned intensity of irradiation isnecessary to have the desired decomposing effect; thus, it is advisableto re ulate the velocity of the high speed electrons used fordetoxification and the length of each irradiation period and theirnumber in such a manner as to obtain the above indicated totalintensity, i. e. to obtain an irradiation by which on the average eachof the alkaloid particles is hit during consecutive irradiation periodstogether by electrons having the above indicated total intensity of 10*of a watt.

I may u e for my new processes described above different types ofdevices for creating high speed electrons and also the most differentlyconstructed and shaped irradiation chambers. However, I have found thatthe devices described in my U. 8. Patents Nos. 2,043,733 and 2,099,327are very well adapted and the most eflicient ones for the purposes of mypresent invention. Thus, while any source of radiation can be used forthe production of high speed electrons, my so-called condenser methodwhich generates electric impulses of very short duration and greatintensity by use of a laminated discharge tube proved most satisfactory.This method consists in using a plurality of condenser units, the numberof which is selected according to the voltage required, charging thesecondenser units in parallel over charging resistances and dischargingthem by means of discharge spark gaps in series whereby the voltage ismultiplied in accordance with the number of condenser units employed andin accordance with the voltage with which each of the individualcondenser units has been charged.

This high voltage, which is at least one million volts, preferablyhowever four or more million volts, is conducted to the cathode of alaminated discharge tube also described in my above mentioned U. S.patents. A discharge tube of this type is adapted to create high speedelec trons having the required high velocity and acapted for thedetoxification processes described above.

Although my above described processes are effective for a great varietyof products to be detoxified, it is rather difiicult to obtainsatisfactory results with certain products. Thus, it is not alwayspossible, by increase of the speed of the bombarding electrons anddecrease of the length of the single irradiation periods, to avoidentirely certain of the above listed side effects, namely the creationof hydrogen peroxide, ozone and nitrous oxides, and the denaturation ofproteins contained in some substances. Furthermore, during irradiationof certain substances, additional side reactions occur which cannot beeliminated by the raise of the velocity of the bom barding electrons andby reduction of the length of the single irradiation periods. Suchunaffected side reactions are mainly the destruction of the naturalcoloring matters in the irradiated products, particularly thedestruction of hemoglobin, chlorophylls and carotinoids present in someof the irradiated substances.

I have found that the side reactions listed in the preceding paragraphcan be greatly reduced and in most cases completely avoided by coolingthose products which are affected by such side reactions to a lowtemperature and irradiating the thus cooled products in the mannerdescribed above.

The degree of cooling depends on the character of the single products tobe irradiated: Good results were already obtained by cooling to atemperature of -20 0.; the results were, however, better if the productswere cooled to a tempera.- ture of C., or less, and irradiated at such alow temperature.

Tests proved that by first cooling the products to be detoxified to thelow temperatures mentioned above and then subjecting the thus cooledproducts to a series of very short irradiations by high speed electrons,it is possible to detoxify the stimulant and poisonous substancescontained in certain products for human and animal consumption withoutnoticeable change in appearance, taste and odor.

Generally, I have found that the combination of the three factorsmentioned above, namely high speed electron irradiation, a. series ofvery short irradiation periods. and cooling to a low temperature, notonly suppresses oxidation, but

also avoids all other above discussed side effects. leaving only themost rapidly occurring chemical and biological reactions unaffected.

It should be mentioned that during irradiation of some types of productsto be detoxified with high speed electrons, certain side reactions occurwhich can hardly be avoided by any of my new processes defined above.This holds true, particularly, for products which are highly unstable tooxidation. Cooling to very deep temperatures and very short irradiationperiods, as proposed above, are insufllcient to avoid oxidation of suchproducts durin irradiation.

I have found it advisable to irradiate products of the type defined inthe preceding paragraph in accordance with my present invention in theabsence of oxidizing agents, e. g. in an atmosphere having an oxygenconcentration which is reduced to such a degree that the amount ofoxygen molecules present is insufficient to react during irradiationwith the irradiated products. Such reduction of the oxygen concentrationcan be attained by use of an inert gaseous atmosphere, or by use ofpartial vacuum.

I have found that in order to attain good results, it is'advisable toplace some types of products to be treated in sealed containers and toirradiate the products while they are sealed in such containers. ofcourse, as set forth above, these containers should contain only verylittle or no oxygen at all so as to prevent oxidation of the irradiatedproducts.

In accordance with my present invention, detoxification of products ispreferably carried out in the following way:

First, the product to be detoxified is placed into a container fromwhich the air is removed, either by introduction of an inert gas or byevacuating the container.

After the product to be detoxified is placed into the container and theair removed therefrom as described above, the container is air-tightlysealed.

Thereafter, the container together with the product to be irradiated iscooled to between 0 C. and 100 0., depending upon the type of product.

The thus cooled container and product to be irradiated are thensubjected to irradiation with high speed electrons having a velocityequivalent to between three and six million volts during a series ofconsecutive very short time periods, each lasting between and 10* of asecond. This impulse irradiation is continued until on the average eachpoisonous, e. g. alkaloid particle, present in the irradiated productbefore irradiation is hit by high speed electrons having a totalintensity of at least 10- of a watt.

The above described processes can be employed for a great variety ofproducts for human and animal consumption. Practical tests carried outby irradiating various products with high speed electrons of a velocityequivalent to four million volts during a series of consecutiveirradiation periods, each lasting about l0 of a second, showed thefollowing results:

Coffee, irradiated several times in the manner set forth above, lost itshighly stimulant character by decomposition of the caffeine containedtherein.

Similarly, tea was irradiated twice with high speed electrons of theabove specified velocity and tests showed that the theine contained inthe tea was transformed by the electron bombardment into a neutralnon-stimulant and nonpoisonous compound.

Finally, electron bombardment of tobacco for a longer time periodresulted in elimination of the poisonous characteristic of the nicotincontained therein.

Above tests show that the new processes proposed by me are well adaptedfor detoxification of a great variety of products for human and animalconsumption.

It should be mentioned that some of the above described tests werecarried out at low temperatures, i. e. the various products were cooledbefore irradiation. Some of the tests were carried out in an inertpreferably gaseous atmosphere, some were carried out in a partialvacuum, and some were carriedout under pressure, e. g. gas pressure. Ihave also found that in some cases,-e. g. detoxifying of tobacco, it ispreferable to carry out the bombardment with high speed electrons whilethe tobacco leaves are at an elevated temperature. It was also foundthat in some other cases, reduction of the temperature and avoidance ofoxidizing substances greatly improved the detoxifying effects bypreventing undesired side reactions.

It will be understood that each of the elements described above, or twoor more together, may also find a useful application in other types ofprocesses differing from the processes described above. Thus, forinstance, my new process is also adapted to detoxify theobrominecontained in cocoa.

While I have described the invention as embodied in processes fordetoxifying various products, I do not intend to be limited to thedetails shown, since various modifications and changes may be madewithout departing in any way from the spirit of my invention.

Without further analysis, the foregoing will so fully reveal the gist ofmy invention that others can by applying current knowledge readily adaptit for various applications without omitting features that, from thestandpoint of prior art, fairly constitute essential characteristics ofthe generic or specific aspects of this invention, and, therefore, suchadaptations should and are intended to be comprehended within themeaning and range of equivalence of the following claims. I

What I claim as new and desire to secure by Letters Patent is:

1. Method of detoxifying alkaloid-containing products for human andanimal consumption. without substantially affecting the taste, odor andappearance of said products by bombarding the same with high speedelectrons of a velocity equivalent to more than one million volts duringat least one very short time period lasting less than 10- of a second.

2. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products by bombarding the same repeatedly with highspeed electrons of a velocity equivalent to more than one million voltsduring consecutive very short time periods each lasting less than 10- ofa second.

3. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products comprising the steps of cooling the same toa temperature below 0 C.; and bombarding the thus cooled substance withhigh speed electrons of a velocity equivalent to more than one millionvolts during at least one very shorttime period lasting less than 10* ofa second.

4. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products comprising the steps of cooling the same toa temperature below C.; and bombarding the thus cooled substance withhigh speed electrons of a velocity equivalent to more than one millionvolts during consecutive very short time periods each lasting less thanof a second.

5. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products comprising the steps of cooling the same toa temperature of below -50 C.; and bombarding the thus cooled substancewith high speed electrons of a velocity equivalent to more than onemillion volts during at least one very short time period lasting lessthan 10 of a second.

6. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products by bombarding the same in an inert gaseousatmosphere with high speed electrons of a velocity equivalent to morethan one million volts during at least one very short time periodlasting less than 10- of a second.

7. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products by bombarding the same repeatedly in apartial vacuum with high speed electrons Of a velocity equivalent tomore than one million volts during consecutive very short time periodseach lasting less than 10- of a second.

8. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products by bombarding the same in a substantiallyoxygen-free atmosphere with high speed electrons of a velocityequivalent to more than one million volts during at least one very shorttime period lasting less than 10* of a second. 9. Method of detoxifyingalkaloid-containing products for human and animal consumption, withoutsubstantially affecting the taste, odor and appearance of said productscomprising the steps of cooling the same to a temperature below 0 C.;and bombarding the thus cooled substance in a substantially oxygen freeatmosphere with high speed electrons of a velocity equivalent to morethan one million volts during at least one very short time periodlasting less than 10- of a second.

10. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products comprising the steps of placing saidsubstance into a container; air-tightly closing said container; andbombarding said substance air-tightly enclosed in said container withhigh speed electrons of a velocity equivalent to more than one millionvolts during at least one very short time period lasting less than 10-of a second.

11. Method of detoxifying alkaloid-containing products for human andanimal consumption,

without substantially affecting the taste, odor and appearance of saidproducts comprising the steps of placing said substance in a container;air-tightly closing said container; and bombarding said productsair-tightly enclosed in said container with high speed electrons of avelocity equivalent to more than one million volts during consecutivevery short time periods each lasting less than 10- of a second.

12. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products comprising the steps of placing saidsubstance in a container; airtightly enclosing said container; coolingsaid substance air-tightly enclosed in said container to a temperaturebelow 0 C.; and bombarding said cooled product air-tightly enclosed insaid container with high speed electrons of a velocity equivalent tomore than one million volts during at least one very short time periodlasting less than 10- of a second.

13. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products compriisng the steps of placing saidsubstance into a container; airtightly closing said container; coolingsaid substance air-tightly enclosed in said container to a temperaturebelow 0 C.; and bombarding said cooled substance air-tightly enclosed insaid container with high speed electrons of a velocity equivalent tomore than one million volts during consecutive very short time periodseach lasting less than 10- of a second.

14. Method of detoxifying alkaloid-containing products for human andanimal consumption, without substantially affecting the taste, odor andappearance of said products comprising the steps of placing saidsubstance into a container; removing air contained in said container;airtightly closing said container; and bombarding said substanceair-tightly enclosed in said container with high speed electrons of avelocity equivalent to more than one million volts during at least onevery short time period lasting less than 10- of a second.

ARNO BRASCH.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 855,449 Dorn June 4, 19071,275,417 I Gillet Aug. 13, 1918 1,906,402 Newton May 2, 1933 1,907,507Coolidge May 9, 1933 1,952,588 Golden Mar. 27, 1934 2,007,765 KnudsenJuly 9, 1935 2,018,599 Brasch c Oct. 22, 1935 2,043,733 Brasch June 9,1936 2,061,960 Coffmann et al Nov. 24, 1936 2,099,327 Brasch Nov. 16,1937 2,122,741 Haddad July 5, 1938 2,161,985 Szilard June 13, 1939FOREIGN PATENTS Number Country Date 154,213 Great Britain Apr. 24, 1922190,512 Great Britain Dec. 8, 1922 299,735 Great Britain Oct. 30, 1928440,023 Great Britain Dec. 12, 1935

1. METHOD OF DETOXIFYING ALKALOID-CONTAINING PRODUCTS FOR HUMAN ANDANIMAL CONSUMPTION, WITHOUT SUBSTANTIALLY AFFECTING THE TASTE, ODOR ANDAPPEARANCE OF SAID PRODUCTS BY BOMBARDING THE SAME WITH HIGH SPEEDELECTRONS OF A VELOCITY. EQUIVALENT TO MORE THAN ONE MILLION VOLTSDURING AT LEAST ONE VERY SHORT TIME PERIOD LASTING LESS THAN 10-4 OF ASECOND.